Manufacture of azo coloring-matters containing a carbazole derivative.



NoDrawing.

uD'erivative, of which the UNITED sTArEs PATENT carton.

HANS BUGHERER, OF BIEBRICH, GERMANY, ASSIGNOR TO THE FIRM OF KALLE AND COMPANY, AKTIENGE SELLSCHAFT, OF BIEBRICH, GERMIANY.

MANUFACTURE OF AZO COLORING-MATTERS CONTAINING A CARBAZOLE DERIVATIVE.

To all whom at may concern.

Be it known that I, HANS BUcHEnnR, doctor of philosophy and chemist, subject to the King of Prussia, and residing at Biebrich-on the-Rhine, in the German Empire, have invented certain new and useful Improvements in the Manufacture of A20 Coloring-Matters Containin a Garbazole following is a specification.

If phenyl-hydrazin or its nucleus substitution-products be allowed to react on the 2.5.7 or 2.8.6-amino-naphthol-sulfonic-acids (the two hetero-nucleo beta-amino-derivatives of l-naphthol-3-sul'fonic acid) in the presence of sulfites, or sulfur-dioxid, (compounds containing the sulfurous acid rad1- cal) new compounds are obtained which may be considered as carbazole derivatives of l-naphthol-S-sulfonic acid (see German specification No. 208960 and also J ournal fiir Pmktische Ohemie, vol. 77, page 403 et seq. and vol. 79, page 369 at 5-64.). The following example shows how such a carbazole derivative can be obtained from the Lacid (2-amino-5-naphthol-7-sulfonic acid) 239' grams l-acid are heated on the water bath, or reflux condenser, with 1500 gramsv of bisulfite solution of about 38 Baum, 120 grams of, caustic soda lye of 40 Baum and 150 grams of phenyl-hydrazin until the l-acid has entirely disappeared, or. only traces of it are left, this requiring from about 5 to 10 hours. The mixture is rendered strong alkaline, the excess of phenylhydrazin driven off by steam, and the mass acidified with sulfuric acid or hydrochloric acid, whereupon the sulfur-dioxid is driven off by boiling. In this way a solution of the carbazole compound is obtained, which has probably the following constitution:

By evaporating to dryness the acid solution, the new acid separates in the form of an oil, which is very readily soluble in cold water. With aromatic amins (for example, anilin and para-toluidin) the carbazole derivative forms difiicultly soluble salts, which are suited for its separation. By the formation of carbazole, the l-acid loses the ca Specification of Letters Patent.

- acid Patented Apr. 23, 1912.

Application filed April 1, 1910. Serial No. 552,877.

pacity to couple in with diazo compounds in position 1; if furthermore, the hydroxyl group is closed by acid radicals (carbon dioxid, acetic acid, benzoic acids, and the like), the carbazole derivatives lose the ca pacity for forming azo dyes in a normal manner.

The production of the carbazole derivative from 2-amino-8-naphthol-6-sulfonic (gamma acid) and phenyl-hydrazin is effected in exactly the same manner. As already mentioned, in the condensations with and gamma-acid, the simplest phenylhydrazin can be replaced by other hydrazins, for instance orthoand para-tolyl, or paraamino-phenyl-hydrazin, as Well as their sulfonic acid and earboxylic acid or halogen derivatives, and the like. The carbazole derivative from gamma-acid and phenyl-hydrazin is somewhat more difiicultly soluble in water than the corresponding compound from the I-acid and can therefore be partially precipitated from concentrated solutions by hydrochloric acid, or sulfuric acid. I have now discovered that these carbazole derivatives are suit-able as components for the preparation of azo dyes; according to the action of mono-diazo compounds, tet-razo compounds or diazotized amido-azo compounds, azo dyes are obtained which contain one or more azo groups. and whose shades vary within the widest limits according to the selection of the components.

Example 1. a. The diazo compound obtained from 10.7 kilograms of ortho-toluidin in the usual manner iscaused to run into an alkaline solution containing 34 kilograms of the sodium salt of that carbazole derivative resulting from the combination of phenylhydra'zin, bisulfite and 2-amino-5-naphthol- -7-sulfonic acid. The coupling takes place immediately and is completed in a very short time. The separation of the dye is completed by salting out; it is then filtered, pressed and dried. The dyestufi' dyes wool both in neutral and acid bat-h, as well as cotton in neutral to alkaline bath, in red shades fast to acids. 6. If in the foregoing example, 35.5 kilograms of the sodium salt of that carbazole derivative be used, which is obtained from para-amino-phenyl-hydrazin, bisulfite and 2-amino-5-naphthol-7-sulfonic acid, then a dye is obtained which dyes cotton in shades having a tinge of blue capable of being further developed on the fiber in the usual manner, for instance by diazotizing the amino group of the phenyl-hydrazin nucleus and combining the obtained diazo compound with azo components. It is .obvious that this process can be executed vice versa, 2'. e. by diazotizing at first the carbazole derivative from para-aminoplienyl-hydrazin, bisulfite and 2amino-5- naphthol-7-sulfonic acid, then coupling with azo compounds and finally combining the resulting body with diazo compounds, in this example with ortho-toluidin, directly on the fiber or in absence of it.

In the example under a and b, the diazotized toluidin may be replaced by the diazo compound of other amins, such for instance as chlor-anilin, xylidin, acetyl-para-phenylene-diamin, naphthyl-amin, sulfanilic acid and the like. On the other hand the carbazole derivatives used can be replaced by such as are obtained by the action of substituted aryl-hydrazins on 2-amino-5-naphthol-7-sulfonic acid.

Example 2'. If in the above example the solution of diazo-toluidin be replaced by the tetrazo compound prepared 1n the usual manner from 9.2 kilograms of benzidin and the process be continued as usual, a dye is obtained which dyes cotton in violet shades.

Example 3: The amino-azo compound obtained in the usual way from 19.5 kilograms of metanilic acid and 14.3 kilograms of alnha-naphthyr-amin is diazotized and filtere off. Then the diazo compound is introduced into a soda-alkaline solution which contains 34 ln'lograms of the carbazole derivati'v' obtained in the hereinbefore described manner from the I-acid and phenyl hydrazin. The solution is stirred for some time, then heated, and the dye separates out on the addition of common salt. It produces on wool, deep violet shades. In the same manner other secondary disazo dyes can be manufactured. The dye obtained from naphthionic acid and alpha-naphthylamin dyes on wool a violet blue shade. Similarproperties are possessed by the dye obtained from l-naphthyl-amim3.6-disulfonic acid and alpha-na'phthyl-amin. The dye from1-amino-8-naphthol-3.6-disu1fonic acid, alpha-naphthyl-amin and the carbazole derivative produces on cotton violet blue shades.

If in the above examples the carbazole derivatives of I-acid be replaced by'the carbazole derivative of the 2.8.6-amino-naphtholsulfonic acid (gamma acid) dyes are obtained which, compared with the azo'dyestufis obtained by combination of di-azo components with the non-carbazolized y-acid, are distinguished by the clearness of their shade and their fastness. Of especial interest are the dyes which are obtainable in the usual manner from the so-called para-diamins, such for instance as the dye from salicylic acid, benzidin and the carbazole compound of gamma-acid and phenyl-hydrazin, also the dye from the lastunen'tioned carbazole compound of gamma-acid, benzidin and resorcinol, or the corresponding dyes in which the resorcinol is replaced by meta-diamins or a1nino phen0ls and their derivatives. The favorable influence of carbazolization is moreover very perceptible in monoand secondary disazo dyes. Thus by diazotizing para-aminosalicylic acid and coupling it with the carbazole derivative from gammaacid and phenylhydrazin, a dye is obtained which dyes wool from the neutral bath BordeauX-red shades which can be developed in the usual manner by means of chromium salts. With the secondary disazo dyes, the increased aflinity for cotton which is due to carbazolization is a most surprising one, for instance the dyestufi from aminoazo-benzo-sulfonic acid and the carbazole compound from gamma-acid and. phenylhydrazin presents in neutral bath almost as great an aflinity for cotton fiber as for wool, so that this dyestufl appears suitable for the production of powerful Bordeaux shades on half wool. Even the secondary disazo dye from naphthionic acid, 1.7-naphthyl-aminsulfonic acid and the carbazolized gamma-acid possesses in a marked degree in spite of the three sulfonic groups, the properties-of a cotton dyestufl.

The following examples illustrate the manner in which the process can be carried out:

Example I: The tetrazo compound obtained from 184 kilograms of benzidin is at first coupled with one molecule of salicylic.

acid in soda-alkaline-solution. After the intermediate product is formed, a soda-alkaline solution of the calculated quantity of carbazolized gamma-acid is allowed to run into the reaction mass. The disazo dye is readily formed, it is separated from the reaction mixture almost completely and is worked upon in the usual manner. It dyes cotton fine and fast reddish-brown shades. Example II: If the tetrazo compound obtained from one molecule of benzidin in soda-alkaline solution be first allowed to re act on one molecule of carbazolized gamma-acid and if, after the intermediate product is formed, it be allowed to react on one molecule of resorcinol, a violet dye is obtained which can be developed to a fine, fast brown on the fiber by means of .diazotized para-nitranilin. Dyes having quite similar properties are obtained when the resorcinol is replaced for instance by metaphenylene-diamin or metatoluylenediamin, and the second coupling is efiected in a weak solution of acetic acid. They dye cotton fiber direct reddishand violet-brown shades respectively; by developing with diazotized para-nitranilin the tone becomes a markedly deeper brown and the fastness to washing is increased. The two other above named dyes om para-amino-salicylio acid or aminoazo-benzo-sulfonic acid are likewise obtained in a normal manner by the coupling of carbazolized gamma-acid in soda-alkaline solution.

What 1 claim is:'

1. The process for producing azo coloring matters which consists in treating heteronucleo-beta-amino derivatives of l-naphthol 3-sulfonic acid with aryl-hydrazins in presence of a compound containing the sulfurous acid radical and combining the obtained products with diazo compounds.

2. The process for producing azo coloring matters which consists in treating 2-amino- 5-naphthol- 7-sulfonic acid with an aryl-hydrazin in the presence of a compound containing the sulfurous acid radical and combining the obtained carbazole compound with a diazo compound.

8. Process for producing azo coloring matters which consists in treating 2-amino- 5-naphthol-f7-sulfonic acid with phenylhydrazin in presence ofa compound containing the sulfur'ous acid radical and combining the obtained carbazole compound with 4. As new compositions of matter the dye stuffs obtained from the carbazole derivatives of the hetero-nucleal beta-amino derivadiazotized xylidin. t

ti ves of 1-naphthol-3-sulfonic acid with diazo compounds constitut' g in dry state red to brown to black more or less crystalline powders, soluble in water with a yellowish-red-to bluish-green color; soluble in concentrated sulfuricacid with a violet-blue to dark-green color, this solution separating, rownish-red to bluish-green ether, ligroin, orming when. treated with reducing agents as essential constituent the carbazole Genie! of this patent may be obtained m five cents 'Witnesses:

derivative of the 2-amino-1-oxynaphthalene- 3-sulfonic acid.

5. As new compositions of matter the dyestufl's obtained from the carbazole derivatives of the 2-amino-5-naphthol-7-sulfonic acid with diazo compounds constituting in a dry state red to brown to black more or less, crystalline powders, soluble in water with a yellowish-red to bluish green color; soluble in concentrated sulfuric acid with a violet-blue to dark-green color, this solution separating when diluted brownish-red to bluish-green flakes, insoluble in benzene, ether, ligroin, and forming when treated with reducing agents as an essential constituent the carbazole derivative of the 2.6- diamino-5-oxynaphthalene-7-sulfonic acid.

6. As a new com osition of matter the dyestufi' consisting of the diazo compound of. ortho-xylidin with the carbazole derivative of the 2-amino-5-naphthol-7-sulfonic acid, constituting in dry state a crystalline brownish-red powder, soluble in water with bluishred color from which solution the free acid is separated by hydrochloric acid in brownish-'red flakes, soluble in alcohol or pyridin with orangered color, soluble in sulfuric acid with violet-blue coloration which solution separates after diluting brownish-red flakes, insoluble in benzene or ether and be ing decomposed when treated with reducing agents into ortho-xylidin on the one hand and the carbazole derivative of the 2.6-diamino-5-oxy-naphthalene-7-sulfonic acid on the other hand. 1

In testimony whereof I have signed my name to this specification in the presence of witnesses.

wo subscribing HANS BUCHERER.

IIERMANN PLISCHKE, MAX Dmncnn.

each, by addressing the Commissioner of Patents,

Washington, D. G. 

